Oil based drilling fluid

ABSTRACT

Invert emulsion compositions including an oleaginous, a non-oleaginous and an amine surfactant that are useful in the oil and gas well drilling art are disclosed. The amine surfactant is selected so that the invert emulsion can be converted form a water-in-oil type emulsion to a oil-in-water type emulsion upon the protonation of the amine surfactant. Deprotonation of the amine surfactant reverses the conversion.

This is a continuation of Ser. No. 08/862,201 filed May 23, 1997 nowU.S. Pat. No. 6,218,342, which claims benefit of Ser. No. 60/023,043filed Aug. 02, 1996.

This application claims the benefit of Provisional Application No.60/023,043 filed Aug. 2, 1996.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to invert emulsion fluids utilized in thedrilling, completion and work over of oil and gas wells.

2. Background

Many types of fluids have been used in the drilling of oil and gaswells. The selection of an oil-based drilling fluid, also known asoil-based mud, involves a careful balance of the both the good and badcharacteristics of such fluids in a particular application, the type ofwell to be drilled and the characteristics of the oil or gas field inwhich the well is to be drilled. A surfactant capable of emulsifyingincorporated water into the oil is an essential component of oil-basedmuds.

The primary benefits of selecting an oil-based drilling fluid include:superior hole stability, especially in shale formations; formation of athinner filter cake than the filter cake achieved with a water basedmud; excellent lubrication of the drilling string and downhole tools;penetration of salt beds without sloughing or enlargement of the hole aswell as other benefits that should be known to one of skill in the art.

An especially beneficial property of oil-based muds is their excellentlubrication qualities. These lubrication properties permit the drillingof wells having a significant vertical deviation, as is typical ofoff-shore or deep water drilling operations or when a horizontal well isdesired. In such highly deviated holes, torque and drag on the drillstring are a significant problem because the drill pipe lies against thelow side of the hole, and the risk of pipe sticking is high when waterbased muds are used. In contrast oil-based muds provide a thin, slickfilter cake which helps to prevent pipe sticking and thus the use of theoil based mud can be justified.

Despite the many benefits of utilizing oil-based muds, they havedisadvantages. In general the use of oil based drilling fluids and mudshas high initial and operational costs. These costs can be significantdepending on the depth of the hole to be drilled. However, often thehigher costs can be justified if the oil based drilling fluid preventsthe caving in or hole enlargement which can greatly increase drillingtime and costs. Disposal of oil-coated cuttings is another primaryconcern, especially for off-shore or deep-water drilling operations. Inthese latter cases, the cuttings must be either washed clean of the oilwith a detergent solution which also must be disposed of, or thecuttings must be shipped back to shore for disposal in anenvironmentally safe manner. Another consideration that must be takeninto account is the local governmental regulations that may restrict theuse of oil based drilling fluids and muds for environmental reasons.

Oil-based muds contain some water, either formed in the formulation ofthe drilling fluid itself, or residual water in the hole, orintentionally added water to affect the properties of the drilling fluidor mud. In such water-in-oil type emulsions, also know as invertemulsions, a emulsifier is utilized that will stabilize the emulsion. Ingeneral, the invert emulsion may contain both water soluble and oilsoluble emulsifying agents. Typical examples of such emulsifiers includepolyvalent metal soaps, fatty acids and fatty acid soaps, and othersimilar suitable compounds that should be known to one of skill in theart. The use of traditional emulsifiers and surfactants in invertdrilling fluid systems can complicate the clean up process in open holecompletion operations. Fluids using traditional surfactant andemulsifier materials may require the use of solvents and othersurfactant washes to penetrate the filter cake and reverse thewetability of the filter cake particles. That is to say the washing withdetergents should convert the oil-wet solids of the filter cake intowater-wet solids. Water-wet solids in the filter cake are necessary sothat the subsequent acid wash can attack the particles of the mud cakeand destroy or remove them prior to production. The productivity of awell is somewhat dependent on effectively and efficiently removing thefilter cake while minimizing the potential of water blocking, pluggingor otherwise damaging the natural flow channels of the formation. Theproblems of efficient well clean-up, stimulation, and completion are asignificant issue in all wells, and especially in open-hole horizontalwell completions.

A typical horizontal well completion process includes one or more of thefollowing: drilling the horizontal section utilizing an oil-baseddrilling fluid; smoothing directional corrections with a hole opener;displacing the open hole section with an unused drill-in fluid tominimize solids exposed to the completion assembly; running thecompletion assembly in to the horizontal well; displacing the drill-influid with a completion brine; washing the filter cake with solvents andsurfactants to remove or wash away the oil-based drilling fluid;destroying the filter cake with an acid soak; and, commencingproduction. Extension of the time required to clean up the open holewell can result in wellbore instability and possible collapse. Thecollapse of a well is generally considered a bad occurrence because thewell will then have to be redrilled or opened up if production from theformation is to occur. Thus the stability of the open-hole well limitsthe number of steps performed before commencing production. Thus thereis a tradeoff between increased production due to a fully cleaned-upwell bore and the potential of well collapse due to instability.

In view of the above there exists an unmet need for an oil-baseddrilling fluid or mud emulsion that can easily be broken in the presenceof the acid soak solution. Such a fluid would allow a decrease in thenumber of steps involved in removing the filter cake and cleaning up thewell which minimizes the risk of well collapse. In addition such a fluidwould allow for a more thorough and complete cleaning up of the wellthus increasing the production of the well.

SUMMARY OF THE INVENTION

Surprisingly, a novel invert emulsion fluid useful in the drilling,completing or working over of a subterranean well has been invented inwhich the emulsion can be readily and reversibly converted from awater-in-oil type emulsion to a oil-in water type emulsion. In oneparticular embodiment, the invert emulsion fluid includes an oleaginousfluid, a non-oleaginous fluid and an amine surfactant having thestructure

wherein R is a C₁₂ to C₂₂ group, R′ is independently selected from H, orC₁ to C₃ alkyl; A is NH or 0 and the sum of x and y is greater or equalto one but less than or equal to three. The oleaginous fluid maypreferably be diesel oil, mineral oil, a synthetic oil and suitablecombinations of these and may include at least 5% of a material selectedform the group including esters, ethers, acetals, dialkylcarbonates,hydrocarbons and combinations thereof. The non-oleaginous fluid ispreferably an aqueous liquid which may be selected from the groupincluding sea water, brine containing organic and/or inorganic dissolvedsalts, an aqueous solution containing water-miscible organic compounds,or combinations of these. In another embodiment of the presentinvention, the invert emulsion fluid may contain a weighting agent, abridging agent or both. Such weighting agents and/or bridging agents maybe selected from the group including calcium carbonate, dolomite,siderite, barite, celestite, iron oxides, manganese oxides, ulexite,carnalite, and sodium chloride.

Yet another embodiment of the present invention includes the method ofconverting the emulsion of the present invention from an invert emulsionto a regular emulsion. In this embodiment, the invert emulsion isadmixed with an acid that is functionally able to protonate the aminesurfactant. When sufficient quantities of the acid are utilized, theinvert emulsion of the present invention is converted so that theoleaginous fluid becomes the discontinuous phase and the non-oleaginousfluid becomes the continuous phase. The conversion of the phases isreversible so that upon addition of a base capable of deprotonating theprotonated amine surfactant, a stable invert emulsion in which theoleaginous liquid becomes the continuous phase and the non-oleaginousfluid become the discontinuous phase can be formed.

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The interfacial tension between an oleaginous fluid, for example oil,and a non-oleaginous fluid, for example water, is often high. Thus, ifthe liquids are mixed together they spontaneously separate from eachother when the agitation ceases, to minimize the interfacial area.Lowering the interfacial tension with a emulsifier enables one liquid toform a stable dispersion of fine droplets in the other. The lower theinterfacial tension, the smaller the droplets and the more stable theemulsion. In most emulsions, the oleaginous fluid is the dispersed phaseand the non-oleaginous fluid is the continuous phase. However, “invertemulsions” in which the non-oleaginous fluid is the dispersed phase andthe oleaginous fluid is the continuous phase, can be formed upon the useof a suitable emulsifier. One of skill in the art should appreciate thatthe chemical properties of the emulsifier are important in the selectionof a suitable emulsifier to form a stable invert emulsion.

The present invention is generally directed to an invert emulsion fluidthat is useful in the drilling, completing and working over ofsubterranean wells, preferably oil and gas wells. Such uses of invertemulsion fluids in such application should be known to one of skill inthe art as is noted in the book COMPOSITION AND PROPERTIES OF DRILLINGAND COMPLETION FLUIDS. 5th Edition, H. C. H. Darley and George R. Gray,Gulf Publishing Company, 1988, the contents of which are herebyincorporated herein by reference.

In one embodiment of the present invention, the invert emulsion fluidincludes an oleaginous fluid, an non-oleaginous fluid and an aminesurfactant. The surfactant component is selected so as to provide theunexpected and unobvious results substantially described herein. When amajority of the amine is in its unprotonated form, an invert emulsionmay be formed in which the oleaginous liquid is the continuous phase andthe non-oleaginous liquid is the discontinuous phase. That is to say,the unprotonated form of the amine surfactant is able to stabilize aninvert emulsion. Upon addition of a protonating agent, herein referredto as an acid, that is capable of protonating a major portion of theamine surfactant, the oleaginous liquid becomes the discontinuous phaseand the non-oleaginous liquid become the continuous phase. In otherwords, the invert emulsion is converted to a regular emulsion upon theaddition of acid and the protonation of the amine surfactant. Further,upon addition of a deprotonanting agent, herein referred to as a base,that is capable of deprotonating a major portion of the protonated aminesurfactant, an invert emulsion may be again formed; that is, the invertemulsion of the present invention is reversible to an oil-in-wateremulsion, and back.

The oleaginous fluid of the present invention is a liquid and morepreferably is a natural or synthetic oil and more preferably theoleaginous fluid is selected from the group including diesel oil;mineral oil; a synthetic oil, such as polyolefins,polydiorganosiloxanes, siloxanes or organosiloxanes; and mixturesthereof. The concentration of the oleaginous fluid should be sufficientso that an invert emulsion forms and may be less than about 99% byvolume of the invert emulsion. In one embodiment the amount ofoleaginous fluid is from about 30% to about 95% by volume and morepreferably about 40% to about 90% by volume of the invert emulsionfluid. The oleaginous fluid in one embodiment may include at least 5% byvolume of a material selected from the group including esters, ethers,acetals, dialkylcarbonates, hydrocarbons, and combinations thereof.

The non-oleaginous fluid used in the formulation of the invert emulsionfluid of the present invention is a liquid and preferably is an aqueousliquid. More preferably, the non-oleaginous liquid may be selected fromthe group including sea water, a brine containing organic and/orinorganic dissolved salts, liquids containing water-miscible organiccompounds and combinations thereof. The amount of the non-oleaginousfluid is typically less than the theoretical limit needed for forming aninvert emulsion. Thus in one embodiment the amount of non-oleaginousfluid is less that about 70% by volume and preferably from about 1% toabout 70% by volume. In another embodiment, the non-oleaginous fluid ispreferably from about 5% to about 60% by volume of the invert emulsionfluid.

The selection of a suitable amine surfactant useful in the presentinvention is accomplished by combining an amount of the unprotonatedamine with portions of the oleaginous fluid and non-oleaginous fluid ina suitable container. The fluid is then vigorously agitated or shearedso as to intimately mix the two fluids. Upon stopping of the mixing,visual observation will determine if an emulsion has formed. An emulsionis considered stable if the oleaginous and the non-oleaginous fluids donot substantially separate after agitation. That is to say the emulsionwill last for more than about 1 minute after the halting of theagitating or shearing motion that formed the emulsion. One test ofwhether or not an invert emulsion has formed is to take a small portionof the emulsion and place it in a container of the oleaginous fluid. Ifan invert emulsion is formed, the drop of emulsion will disperse in theoleaginous fluid. An alternative test is to measure the electricalstability of the resulting emulsion using an commonly available emulsionstability tester. Generally in such tests, the voltage applied acrosstwo electrodes is increased until the emulsion breaks and a surge ofcurrent flows between the two electrodes. The voltage required to breakthe emulsion is regarded in the art as a measure of the stability of theemulsion. Such tests of emulsion stability should be well known to oneof skill in the art as is evidenced by described on page 166 of the bookCOMPOSITION AND PROPERTIES OF DRILLING AND COMPLETION FLUIDS, 5thEdition, H. C. H. Darley and George R. Gray, Gulf Publishing Company,1988, the contents of which are hereby incorporated herein by reference.

In view of the above selection criteria, in one embodiment of thepresent invention the amine surfactant should have the general formula

wherein R is C₁₂-C₂₂; R′ is independently selected from hydrogen or C₁to C₃ alkyl group; A is NH or O, and x+y has a value greater than orequal to one but also less than or equal to three. Preferably the Rgroup may be a C₁₂-C₂₂ aliphatic hydrocarbon and more preferably is anon-cyclic aliphatic. In one embodiment the R group contains at leastone degree of unsaturation that is to say at least one carbon-carbondouble bond. In another embodiment the R group may be a commerciallyrecognized mixture of aliphatic hydrocarbons such as soya, which is amixture of C₁₄ to C₂₀ hydrocarbons, or tallow which is a mixture of C₁₆to C₂₀ aliphatic hydrocarbons, or tall oil which is a mixture of C₁₄ toC₁₈ aliphatic hydrocarbons. In another embodiment, one in which the Agroup is NH, the value of x+y is preferably two with x having apreferred value of one. In yet another embodiment in which the A groupis O, the preferred value of x+y is two with the value of x beingpreferably one. Preferred examples of commercially available aminesurfactants include Ethomeen T/12 a diethoxylated tallow amine; EthomeenS/12 a diethoxylated soya amine; Duomeen O a N-oleyl-1,3-diaminopropane,Duomeen T a N-tallow-1,3-diaminopropane, all of which are available fromAkzo.

The amount of amine surfactant present in the invert emulsion fluid ofthe present invention, as noted above, should be sufficient to stabilizethe invert emulsion according to the above noted test. That is to saythe emulsion will last for more than about 1 minute after the halting ofthe agitation or shearing motion that forms the emulsion. While theconcentration may vary depending on the particular components in thedrilling fluid or mud, typically the concentration is less than about10% by volume of the fluid. Thus in one embodiment the amine surfactantis preferably present in the invert emulsion fluid at a concentration of0.1% to 5.0%. More preferably the amount of amine surfactant presentshould be present in a concentration of 1 to 5% by volume of the fluid.

As previously noted above, it has been unexpectedly found that theaddition of a protonating agent causes the conversion of the invertemulsion, that is to say a water-in-oil type emulsion, into a regular orconventional emulsion, that is to say an oil-in-water type emulsion. Theprotonating agent, herein referred to as an “acid”, must be functionallycapable of protonating the amine surfactant. Further, the acid should beof sufficient strength to protonate the amine surfactant so as to causethe conversion of the emulsion from an invert emulsion to a regularemulsion. In one embodiment this amount is greater than about 1equivalent of acid and preferably is about 0.1 to about 5 equivalents.Compounds that are suitable for use as an acid include, mineral acidsand organic acids preferably soluble in water. Preferred mineral acidsinclude hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid,hydrofluoric acid, hydrobromic acid and the like. Preferred organicacids include citric acid, tartaric acid, acetic acid, propionic acid,glycolic acid, lactic acid, halogenated acetic acids, butyric acid,organosulfonic acids, organophosphoric acids, and the like. Compoundsthat generate acid upon dissolution in water may also be used, forexample, acetic anhydride, hydrolyzable esters, hydrolyzableorganosulfonic acid derivatives, hydrolyzable organophosphoric acidderivatives, phosphorus trihalide, phosphorous oxyhalide, anhydrousmetal halides, sulfur dioxide, nitrogen oxides, carbon dioxide, andsimilar such compounds. Typically, fatty acids should be avoided or usedin small amounts so as to not interfere with the reversibility of theamine surfactant system.

In yet another embodiment of the present invention, other surfactantcompounds may be used in conjunction with the amine surfactants utilizedherein. In such cases it is important however that the quantity andnature of these supplemental surfactants not interfere in the abilityand properties given the emulsion fluid by the amine surfactant to actas described herein.

The fluids of the present invention are especially useful in thedrilling, completion and working over of subterranean oil and gas wells.In particular the fluids of the present invention are useful informulating drilling muds and completion fluids that allow for the easyand quick removal of the filter cake. Such muds and fluids areespecially useful in the drilling of horizontal wells into hydrocarbonbearing formations.

The method used in preparing the drilling fluids of the presentinvention is not critical. Conventional methods can be used to preparethe drilling fluids of the present invention in a manner analogous tothose normally used, to prepare conventional oil-based drilling fluids.In one representative procedure, a desired quantity of oleaginous fluidsuch as a base oil and a suitable amount of amine emulsifier are mixedtogether and the remaining components are added sequentially withcontinuous mixing. An invert emulsion of the present invention is formedby vigorously agitating, mixing or shearing the oleaginous fluid and thenon-oleaginous fluid.

The fluids of the present invention may further contain additionalchemicals depending upon the end use of the invert emulsion so long asthey do not interfere with the reversibility of the invert emulsionfluids described herein. For example, wetting agents, organophilicclays, viscosifiers, weighting agents, bridging agents and fluid losscontrol agents may be added to the fluid compositions of this inventionfor additional functional properties. The addition of such agents shouldbe well known to one of skill in the art of formulating drilling fluidsand muds. However, it should be noted that the addition of such agentsshould not adversely interfere with the properties imparted by the aminesurfactant as described herein.

Wetting agents that may be suitable for use in this invention include,crude tall oil, oxidized crude tall oil, surfactants, organic phosphateesters, modified imidazolines and amidoamines, alkyl aromatic sulfatesand sulfonates, and the like, and combinations or derivatives of these.However, the use of fatty acid wetting agents should be minimized so asto not adversely effect the reversibility of the invert emulsiondisclosed herein. Versawet® and Versawet®NS are examples of commerciallyavailable wetting agents manufactured and distributed by M-I DrillingFluids L.L.C. that may be used in this invention. Silwet L-77, L-7001,L7605 and L-7622 are examples of commercially available surfactants andwetting agents manufactured and distributed by Union Carbide ChemicalCompany Inc.

Organophilic clays, normally amine treated clays, may be useful asviscosifiers in the fluid compositions of the present invention. Otherviscosifiers, such as oil soluble polymers, polyamide resins,polycarboxylic acids and soaps can also be used. The amount ofviscosifier used in the composition can vary depending upon the end useof the composition. However, normally about 0. 1% to 6% by weight rangeare sufficient for most applications. VG-69 and VG-PLUS are organoclaymaterials distributed by M-I Drilling Fluids L.L.C., and Versa-HRP is apolyamide resin material manufactured and distributed by M-I DrillingFluids L.L.C., that may be used in this invention.

Suspending agents suitable for use in this invention includeorganophilic clays, amine treated clays, oil soluble polymers, polyamideresins, polycarboxylic acids, and soaps. The amount of viscosifier usedin the composition, if any, may vary depending upon the end use of thecomposition. However, normally about 0.1% to about 6% by weight issufficient for most applications. VG-69 and VG-PLUS are organoclaymaterials distributed by M-I Drilling Fluids L.L.C., and Versa-HRP is apolyamide resin material manufactured and distributed by M-I DrillingFluids L.L.C., that may be used in this invention.

Weighting agents or density materials suitable for use in this inventioninclude galena, hematite, magnetite, iron oxides, illmenite, barite,siderite, celestite, dolomite, calcite, and the like. The quantity ofsuch material added, if any, depends upon the desired density of thefinal composition. Typically, weight material is added to result in adrilling fluid density of up to about 24 pounds per gallon. The weightmaterial is preferably added up to 21 pounds per gallon and mostpreferably up to 19.5 pounds per gallon.

Fluid loss control agents typically act by coating the walls of theborehole as the well is being drilled. Suitable fluid loss controlagents which may find utility in this invention include modifiedlignites, asphaltic compounds, gilsonite, organophilic humates preparedby reacting humic acid with amides or polyalkylene polyamines, and othernon-toxic fluid loss additives. Typically, fluid loss control agents areadded in amounts less than about 10% and preferably less than about 5%by weight of the fluid.

In view of the above, one of skill in the art should appreciate theusefulness of the above described emulsion fluid. Thus one embodiment ofthe present invention is the use of such invert emulsion fluids in thedrilling, completion and workover of oil and gas wells. Because many ofproperties of the invert emulsion of the present invention are similarto those of conventional invert emulsions, the application of the fluidsshould be straightforward.

One unexpected and unobvious aspect of drilling subterranean wells withthe invert emulsion of the present invention is that well clean-up andwell stimulation are much easier and quicker to carry out, especiallywhen the well penetrates or comes into contact with a producingformation. As described above, when a conventional invert emulsiondrilling fluid is used, cleaning up and stimulating the well may includewashing the filter cake with detergents and an acid wash to dissolve thefilter cake particles. If these operations are to be fully effective, asignificant amount of aqueous detergent and aqueous acid may penetratethe formation resulting in water blockages in the formation whichadversely affect production. In addition, time is of the essence whenopen hole operations are being conducted because the hole can collapseunexpectedly. Thus, in one embodiment of the present invention an invertemulsion fluid as described above is used in the drilling, completionand workover of a well. When the fluid comes into contact with aproducing formation a filter cake is formed in a conventional manner.However, instead of washing the hole with a detergent solution prior toacid washing, the use of the drilling fluid of the present inventionallows for the use of only an acid containing washing solution. Thus,the acid in the acid washing solution, the acid being functionally ableto protonate the amine surfactant, is injected into the well so as toconvert the emulsion on the filter cake which initially is awater-in-oil type emulsion, into an oil-in-water type emulsion. The acidprotonates the amine and the previously oil-wet particles of the filtercake thereby become water-wet allowing the acid to readily reach anddissolve the acid soluble solids in the filter cake. Thus the removal ofthe oil based filter cake is easier and the process of cleaning-up orstimulating the well is able to be done more effectively and rapidly.

Another unexpected and advantageous benefit of the present invention isthe ability to effectively wash drill cuttings of the oil based drillingfluid. As noted above, this is conventionally done with strong detergentsolutions that do not allow for the recovery and reuse of the drillingoil. In fact seemingly “oil-free” cuttings can contain up to 30% oilabsorbed to the particle surface of the cuttings. The present inventionallows for the replacement of some or all of the detergent solutionswith an acid containing solution as a washing fluid for the cuttings. Insuch an embodiment, the well would be drilled using the drilling fluidsand muds described herein. The resulting cuttings would be separatedfrom the fluid using conventional solids removal methods. The cuttingswould then be contacted at least once with an acid solution so as toinvert the emulsion coating the cuttings. That is to say the washingwith acid causes the cuttings to convert from being oil-wet to water-wetsolids allowing the substantial removal of the oleaginous liquid fromthe cuttings. Once substantially free of oleaginous liquid, the cuttingsmay be further processed or disposed of. It is possible to recover theoleaginous fluid from the acid wash. In such an embodiment the spentacid wash fluid is admixed with a base solution, thus deprotonating theamine surfactant. This facilitates the recovery of the amine surfactantand the oleaginous fluid which may then be reused in the drillingoperation. One of skill in the art should appreciate the benefits ofsuch a system in that the oleaginous fluid is substantially removed fromthe cuttings and the oleaginous fluid can be recovered for reuse in thedrilling operation.

Another embodiment of the present invention is a method for the recoveryand recycling of the oleaginous fluid in a used oil based drillingfluid. In such a method, the invert emulsion fluids as described hereinare used as the drilling, completing, or workover fluid in a well. Theused invert emulsion fluid is admixed with an acid, the acid beingfunctionally able to protonate the amine surfactant and being insufficient quantities so as to convert the invert emulsion to a regularemulsion. That is to say, the addition of the acid protonates the aminesurfactant and the water-in-oil type emulsion utilized in drilling thewell is converted into a oil-in-water type emulsion. Solids, nowsubstantially water-wet, may now be separated from the fluid by gravityor mechanical means for further processing or disposal. The fluid maythen be mixed with a base, the base being functionally able todeprotonate the protonated amine surfactant. The base should be insufficient quantities so as to convert the oil-in-water type emulsionformed upon the addition of acid, back to a water-in-oil emulsion. Theresulting water-in-oil emulsion may then be used as it is orreformulated into a drilling fluid suitable for the drilling conditionsin another well.

The following examples are included to demonstrate preferred embodimentsof the invention. It should be appreciated by those of skill in the artthat the techniques and compositions disclosed in the examples whichfollow represent techniques discovered by the inventors to function wellin the practice of the invention, and thus can be considered toconstitute preferred modes for its practice. However, those of skill inthe art should, in light of the present disclosure, appreciate that manychanges can be made in the specific embodiments which are disclosed andstill obtain a like or similar result without departing from the spiritand scope of the invention.

GENERAL INFORMATION RELEVANT TO THE EXAMPLES

These tests were conducted in accordance with the procedures in APIBulletin RP 13B-2, 1990. The following abbreviations are sometimes usedin describing the results of experimentation.

“PV” is plastic viscosity which is one variable used in the calculationof viscosity characteristics of a drilling fluid, measured in centipoise(cp) units.

“YP” is yield point which is another variable used in the calculation ofviscosity characteristics of drilling fluids, measured in pounds per 100square feet (lb/100 ft²).

“AV” is apparent viscosity which is another variable used in thecalculation of viscosity characteristic of drilling fluid, measured incentipoise (cp) units.

“GELS” is a measure of the suspending characteristics, or thethixotripic properties of a drilling fluid, measured in pounds per 100square feet (lb/100 ft²).

“API F.L.” is the term used for API filtrate loss in milliliters (ml).

“HTHP” is the term used for high temperature high pressure fluid loss,measured in milliliters (ml) according to API bulletin RP 13 B-2, 1990.

Example1

Invert-drilling fluids are prepared according to the followingformulations with an oleaginous fluid to non-oleaginous fluid-ratio of70/30. All the materials are in grams.

Formulations

Material Mud 1 Mud 2 Mud 3 I.O. C₁₆-C₁₈ 125.2 125.2 125.2 Lime 2.0 2.02.0 VG-PLUS 2.0 2.0 2.0 NOVAMUL 10.0 — — Emphos PS-2227 — 5.0 — EthomeenT/12 — — 10.0 25% CaCl₂ Brine 90 90 90 CaCO₃ 293 293 293

In the above table, I.O. C₁₆-C₁₈ is an isomerized olefin available fromAmoco; VG-PLUS is an organophilic clay available from MI DrillingFluids; NOVAMUL is a amidoamine surfactant available from M. I. DrillingFluids; Emphos PS 2227 is a phosphate ester surfactant available fromWitco Chemicals; Ethomeen T/12 is a ethoxylated tallow amine availablefrom Akzo Chemicals; and all other components are technical gradechemicals commonly available.

The following general procedure was used in mixing the mud formulations:First the oil (IO-C₁₆-C₁₈), lime and organophilic clay were mixed for 15min. on a Hamilton Beach Mixer in a suitable mixing jar. Emulsifier wasadded and the combination was further mixed for 10 min. Thecalcium-chloride brine was then added and mixed for 15 min. The weightmaterial (CaCO₃) was added and then jar contents were mixed for 20 min.The initial and heat aged fluid properties were measured at theindicated temperatures.

The following rheologies were measured at room temperature after theabove formulated fluids were heat aged at 150° F. for 16 hours:

Mud 1 Mud 2 Mud 3 Plastic Viscosity (PV) 44 36 41 Yield Point (YP) 13 428 Gel Strength 10 sec. 6 3 8 10 min. 8 5 12 Electrical Stability (E.S.)516 303 244

The above fluids were further heat aged at 250° F. for 16 hours. Uponcooling, the fluids were mixed for 15 min. and the following Theologicalproperties were measured at room temperature:

Mud-1 Mud-2 Mud-3 Plastic Viscosity (PV) 49 45 51 Yield Point (YP) 32 439 Gels 10 sec. 15 2 16 10 min. 15 3 21 Electrical Stability (E.S.) 552205 322

Upon review of the above results, one of skill in the art shouldunderstand that stable drilling fluid formulations can be preparedutilizing amine emulsifiers of the present invention.

Each mud formulation was treated with 10.0 ml of 17.5% hydrochloric acidsolution and stirred for an additional 10 min. Mud 1 and mud 2 remainedinvert oil-base muds as indicated by measured electrical stabilities of453 and 359 respectively. However, mud 3 formulated in accordance withthis invention, was converted so that the non-oleaginous fluid, in thiscase brine, became the continuous phase and the oleaginous fluid becamethe internal phase. As a result the mud became thick. Thewater-continuous phase was indicated by a measured electrical stabilityof seven and the fluid was dispersible in water.

One of ordinary skill in the art should understand and appreciate thatthe above results indicate that conventional emulsifiers can not bereadily converted to water-base mud upon the addition of acid. However,the amine emulsifier of this invention upon protonation, can result inthe conversion of a water-in-oil type emulsion to an oil-in-water typeemulsion.

The hydrochloric acid treated mud 3 was then treated with 5.0 g lime(Ca(OH)₂) and stirred for 15 min. The following rheological propertieswere obtained after treatment with lime.

PV. 53 YP. 7 Gels 10 Sec. 2 10 Min. 3 E.S. 609

In view of the above results, one of skill in the art should realizethat upon deprotonation of amine-surfactant of this invention the fluidcan be converted back from oil-in-water type emulsion to water-in-oiltype emulsion.

Example2

The following invert-drilling fluids were prepared according to thefollowing formulations with an oleaginous fluid to non-oleaginous fluidratio of 50/50.

Formulations

Material Mud 4 Mud 5 Mud 6 Mud 7 Mud 8 IO- 121 121 121 121 121 C₁₆-C₁₈Lime 1.0 1.0 1.0 1.0 1.0 VG-PLUS 2.0 2.0 2.0 2.0 2.0 Surfactant EthomeenEthomeen Duomeen 0 Duomeen T NOVA- T/12 S/12 MUL (grams) (12.0) (120)(12.0) (12.0) (12.0) 25% 200 200 200 200 200 CaCl₂ Brine Calcium 61 6161 — — Carbonate Barite — — — 66 66

In the above table the terms and abbreviations are the same as inExample 1. In addition the terms Ethomeen S/12 is an ethoxylated soyaamine available from Akzo Duomeen O is a N-oleyl-1,3-diaminopropaneavailable from Akzo Chemical; Duomeen T is a N-tallow-1,3-diaminopropaneavailable from Akzo; and all other components are technical gradechemicals commonly available.

The above mud formulation were mixed according to the general proceduredescribed previously in Example 1. The following initial properties weremeasured at room temperature.

Mud 4 Mud 5 Mud 6 Mud 7 Mud 8 P.V. 43 42 32 35 42 YP. 12 19 4 9 21 Gels10 Sec. 5 6 2 5 8 10 Min. 7 8 3 6 10 E.S. 880 496 727 452 150

The above muds were heat aged at 150° F. for 16 hours. The followingTheological properties were then measured at room temperature.

Mud 4 Mud 5 Mud 6 Mud 7 Mud 8 P.V. 43 44 30 36 35 YP. 13 15 9 10 15 Gels10 Sec. 6 6 3 5 6 10 Min. 7 7 4 7 10 E.S. 552 268 450 392 223

In view of the above data, one of skill in the art would recognize thatstable invert emulsion muds can be prepared utilizing variousemulsifiers including those of this invention.

The above heat aged muds 4-8 were treated with 15 ml. of 17.5%hydrochloric acid solution. After mixing for 10 min. the following datawere obtained.

Mud 4 Mud 5 Mud 6 Mud 7 Mud 8 P.V. 22 27 31 to 30 YP. 1 1 9 thick 8 Gels10 Sec. 2 1 9 water-wet 3 10 Min. 2 1 8 Barite 2 E.S. 5 7 6 6 216Comments Water-wet Water-wet Water-wet Water-wet Oil-wet

In view of the above data, one of skill in the art would realize thefollowing: mud formulations 4-7 with amine surfactant of the presentinvention converted to oil-in-water type emulsions when treated withacid; mud formulation 8, which is representative of a conventionaldrilling fluid remained a water-in-oil type emulsion. These conclusionsare supported by reviewing the electrical stability data in which thesingle digit values of mud formulations 4-7 indicate a water continuousphase. In contrast, the electrical stability data of mud formulation 8having a value of 216 indicates that the oil remains the continuousphase.

Treatment of formulations 4-7 each with 5.0 grams of lime and stirringfor 10 min. converted back to water-in-oil type emulsions. The followingare the electrical stability and rheological data of formulations 4-7after such treatment:

Mud 4 Mud 5 Mud 6 Mud 7 ES. 585 523 123 352 P.V. 65 59 — 35 YP. 24 16 —16 Gels 10 Sec. 5 4 — 6 10 Min. 7 5 — 9

One of skill in the art, upon review of the above data should appreciatethat upon protonation of amine surfactants of this invention thewater-in -oil type emulsion fluids can be converted to oil-in-water typeemulsions. In addition, upon deprotonation of the protonated aminesurfactants the oil-in-water type emulsions can be reconverted intowater-in-oil type emulsions.

Example3

The following demonstrate the utility of amine emulsifiers of thisinvention in combination with other emulsifiers.

Formulations

Material Mud 9 Mud 10 Mud 11 Mud 12 IO-C₁₆-C₁₈ 125 125 125 125 Lime 2 22 2 Organoclay 4 4 4 4 EthomeenT/12 10 10 8 6 Wetting Agent EmphosVERSAWET NOVAMUL-3, Monamide- PS2227 NOVAWET-1 150ADY 1.5 1.5 1.5 4Brine 25% 90 90 90 90 CaCl₂ CaCO₃ 291 291 291 291

In the above table the terms and abbreviations are the same as inprevious examples. In addition, the terms VERSAWET is a oxidized crudetall oil available from MI Drilling; NOVAWET is a wetting agentavailable from MI Drilling; Monamide-150ADY is available from MonaChemicals; and all other components are technical grade chemicalscommonly available.

Mud formulations 9-12 were prepared in a manner described above inExample 1.

After recording the initial electrical stability of mud formulations9-12, the muds were heat aged at 250° F./16 hours. The following resultswere obtained on these mud formulations:

Mud 9 Mud 10 Mud 11 Mud 12 Initial E.S. 396 377 368 277 Heat Aged E.S.525 375 310 350 P.V. 66 57 55 62 Y.P. 8 15 16 9 Gels 10 Sec. 6 7 6 7 10Min. 6 8 7 7

To a 35 ml portion of the above mud formulations 9-12, 2.0 ml of glacialacetic acid was added to protonate T/12 amine surfactant. The aceticacid treated samples were thick and converted rapidly to oil-in-watertype emulsions. The electrical stability values for each of the acidtreated samples were six or lower. One of skill in the art willappreciate that such low electrical stability indicates that the wateris the continuous phase, that is to say a oil-in-water emulsion formed.In addition, the acid treated mud formulations 9-12 werewater-dispersible.

The remaining portion of mud formulations 9-12 were contaminated with 25ppb Rev-Dust a simulated drilled solids material, and further heat agedat 250° F./16 hours.

The following heat aged properties were measured on these samples:

Mud 9 Mud 10 Mud 11 Mud 12 ES. 426 486 400 687 P.V. 85 88 76 84 YP. 1720 19 6 Gels 10 Sec. 6 8 8 7 10 Min. 7 12 11 9 High Temp 7.0 6.0 4.4 4.0High Pressure Fluid Loss at 200° F.

The above heat-aged and Rev-Dust contaminated samples were furthercontaminated with 17.5 ml of sea-water, mixed for 30 min. and heat agedat 250° F./16 hours.

The following rheological properties were measured for the resultingsamples:

Mud 9 Mud 10 Mud 11 Mud 12 ES. 980   2000+   2000+ 780 P.V. 100 107 9383 YP. 29 32 36 18 Gels 10 Sec. 11 12 11 9 10 Min. 20 17 14 10

To the resulting muds, 50% by volume of water and 10 g of glacial aceticacid were added and the mixture stirred for 10 min. The electricalstability value for each sample was six or less. In addition the mudswere dispersible in water indicating that water was continuous phase.

Given the above results, one of skill in the art should realize thatinvert emulsion drilling fluids can be prepared utilizing the aminesurfactants of this invention in combination with other conventionalsurfactants. In addition, these fluids can tolerate the addition ofcommon contaminants and can still be converted from water-in-oil typeemulsions to oil-in-water type emulsions upon protonating the aminesurfactants.

Example4

The following mud formulations were prepared to demonstrate the use ofdifferent oleaginous materials using the amine surfactants of thepresent invention.

Formulations

Material Mud 13 Mud 14 Mud 15 Mud 16 Oil LVT-200 dioctyl carbonateDiesel Sarapar-147 (gm) (120) (120) (120) (120) Lime 1.0 1.0 — 1.0VG-PLUS 2.0 2.0 2.0 2.0 Ethomeen T/12 12 12 12 12 25% CaCl₂ Brine 190190 190 190 CaCO₃ 66 66 66 66

In the above table the terms and abbreviations are the same as inprevious examples. In addition the terms, LVT-200 is a mineral oilavailable from CONOCO Oil Co. dioctyl carbonate is available fromHuntsman Chemical; Sarapar-147 is a paraffin hydrocarbon available fromShell Oil Company (Singapore); and all other components are technicalgrade chemicals commonly available.

The above muds were made in accordance with the procedure given above inExample 1.

The following initial rheologies were measured at 120° F.

Mud 13 Mud 14 Mud 15 Mud 16 ES. 229 512 239 313 P.V. 21 53 41 34 YP. 16124 31 7 Gels 10 Sec. 8 60 13 4 10 Min. 8 61 17 5

The above mud formulations were heat aged at 150° F./16 hours. Thefollowing rheologies were measured at 120° F.

Mud 13 Mud 14 Mud 15 Mud 16 ES. 279 35 299 245 P.V. 27 thick 45 29 YP.10 32 8 Gels 10 Sec. 6 15 6 10 Min. 7 17 7

The above mud formulations were treated with 10 ml of 17.5% hydrochloricacid solutions. The electrical stability of each formulation dropped tosix and became water dispersible. One of skill in the art would readilyappreciate that this information indicated that the initial water-in-oiltype emulsion formed was converted to an oil-in-water type emulsion uponthe protonation of the amine surfactant.

Upon treating with 4.0 ml of 50% sodium hydroxide or 5.0 g of lime, theabove acid treated mud formulations converted back from beingoil-in-water type emulsions to water-in-oil type emulsions. Theelectrical stability of these alkali treated muds were as follow:

Mud 13 Mud 15 Mud 16 E.S. 552 543 512

Upon treatment with either hydrochloric-acid, acetic acid or lacticacid, the fluids converted to oil-in-water type emulsions withelectrical stability of six. Treating the acid treated emulsions with4.0 ml of 50% sodium hydroxide, converted the oil-in-water type emulsioninto a water-in-oil type emulsion with E.S. of 500, or greater.

One of skill in the art should appreciate that the above resultsindicate that various types of oleaginous materials can be used toformulate invert emulsion fluids of the present invention. In addition,these invert emulsions can be converted to regular emulsions and back toinvert emulsions by protonating and deprotonating the amine usingvarious water-soluble acids and base.

Example 5

To demonstrate the utility of various acids in protonating theamine-surfactant of this invention the following formulations wereprepared.

Formulations

Material Mud 17 Mud 18 Sarapar-147 120 120 Lime 1 1 VG-PLUS 2.0 2.0Ethomeen-T/12 120. 120. 25% CaCl₂ Brine 190 190 Emphos-PS-2227 0.8 —VERSAWET — 2.20 Barite 66. 66.

In the above table the terms and abbreviations are the same as inprevious examples.

The above muds were made in accordance with the procedure given above inExample 1.

The above formulations were heat aged at 150° F./16 hours. The followingrheologies were measured at room temperature:

Mud 17 Mud 18 E.S. 380 470 PV 26 26 YP 12 9 Gels 10 sec. 6 5 1-Min. 6 6

The above mud formulations were further heat aged at 250° F. for 16hours. The following is the rheologic properties at room temperature:

Mud 17 Mud 18 E.S. 606 750 PV 33 30 YP 9 11 Gels 10 Sec. 4 4 10 Min. 5 5

Mud 17 was treated with 6 g. of solid citric acid. After 1.5 hours ofmixing the electrical stability was measured and had a value of six. Oneof skill in the art should readily appreciate that such a low electricalstability value indicated that the previously formed water-in-oil typeemulsion mud was converted to a oil-in-water type emulsion mud upon theaddition of the citric acid.

Mud 18 was treated with 6.0 g. of glycolic acid. After a thorough mixingthe electrical stability was measured and had a value of six. One ofskill in the art should readily appreciate that such a low electricalstability value indicated that the previously formed water-in-oil typeemulsion mud was converted to a oil-in-water type emulsion mud upon theaddition of the glycolic acid.

Upon treatment with 5.0 g. lime or 4.0 ml of 50% NaOH both theformulations converted back to water-in-oil type emulsions each havingan electrical stability of 608 and 808 respectively.

Example6

The following formulation was prepared to demonstrate the utility ofamine emulsifiers of this invention in making higher mud weightformulations using barite.

Formulations

Material Mud 19 IO-C₁₆-C₁₈ 147.6 Lime 2.0 VG-PLUS 4.0 Ethomeen-T/12 10Emphos PS-2227 1.5 CaCl₂ Brine 25% 106 Barite 276

In the above table the terms and abbreviations are the same as inprevious examples.

The mud formulation was prepared in a manner described above in Example1.

The following rheologies were measured at room temperature before andafter heat aging at 150° F. for 16 hours.

Initial Heat Aged E.S. 632 525 P.V. 40 45 Y.P. 6 7 Gels 10 Sec. 5 5 10Min. 6 7

Upon treating the above formulations with 10 ml 17.5% hydrochloric acidthe electrical stability dropped to 6. The mud was too thick to measurethe Theological characteristics. The heat aged mud was found to bewater-dispersible. One of skill in the art should readily appreciatethat such a low electrical stability value and the water-dispersiblecharacteristic of the heat aged mud indicate that the previously formedwater-in-oil type emulsion mud was converted to an oil-in-water typeemulsion mud upon the addition of the acid.

Treatment of the mud/acid mixture with 5.0 g. lime converted theoil-in-water type emulsion back to a water-in-oil type emulsion asevidenced by the measurement of an electrical stability of 189.

Example 7

The following formulations were prepared to demonstrate the utilizationof fatty acid ester and dialkylcarbonate as oleaginous material inpreparing the mud formulations of this invention.

Formulations

Material Mud 20 Mud 21 Fina Green 188 — Mixed dialkyl carbonate — 188Lime 1.0 1.0 Organophilic Clay 2.0 2.0 T/12 12.0 12.0 25% CaCl₂ Brine 9898 CaCO₃ 76 76

In the above table the terms and abbreviations are the same as inprevious examples. In addition the terms, Fina Green is a fatty acidester available from Fina Petroleum Corp.; Mixed dialkylcarbonate is amixture of aliphatic dialkyl carbonates available from EnichemChemicals; and all other components are technical grade chemicalscommonly available.

The mud formulations were prepared in a manner described above inExample 1.

The above formulations, mud 20 and mud 21 were heat aged at 150° F. for16 hours. The heat aged rheologies were measured at 100° F.

Mud 20 Mud 21 E.S. 884 645 P.V. 89 53 Y.P. 37 18 Gels 10 Sec. 22 10 10Min. 27 14

The above mud formulations when treated with 10 ml of 17.5% hydrochloricacid, electrical stability values dropped to 18. Both mud formulationwere water dispersible. One of skill in the art should readilyappreciate that such a low electrical stability value and thewater-dispersible characteristic of the heat aged mud indicate that thepreviously formed water-in-oil type emulsion mud was converted to anoil-in-water type emulsion mud upon the addition of the acid.

Upon treatment with 5.0 g. of lime both mud formulation becamewater-in-oil type emulsions as evidenced by the oil dispersiblecharacter of the emulsions and electrical stability values of 485. Oneof skill in the art should appreciate that the above demonstrates thatthe water-in-oil emulsion character of the originally formulated invertemulsion was restored by the addition of the lime which deprotonated theamine surfactant.

While the compositions and methods of this invention have been describedin terms of preferred embodiments, it will be apparent to those of skillin the art that variations may be applied to the process describedherein without departing from the concept, spirit and scope of theinvention. All such similar substitutes and modifications apparent tothose skilled in the art are deemed to be within the spirit, scope andconcept of the invention as it is set out in the following claims.

What is claimed is:
 1. An invert emulsion fluid having utility fordrilling, completing, or working over subterranean wells, said fluidcomprising: a) an oleaginous fluid; b) a non-oleaginous fluid; c) aweighting material; d) an amine surfactant having the structure

 wherein R is a C₁₂-C₂₂ aliphatic hydrocarbon; R′ is an independentlyselectable from hydrogen or C₁ to C₃ alkyl; A is NH or O, and 1 <x+y<3;and e) a bridging agent.
 2. The invert emulsion fluid of claim 1 whereinsaid oleaginous fluid comprises from about 30% to about 99% by volume ofsaid fluid.
 3. The invert emulsion fluid of claim 1 wherein saidoleaginous fluid is selected from a group consisting of diesel oil,mineral oil, a synthetic oil, and combinations thereof.
 4. The invertemulsion fluid of claim 1 wherein said oleaginous fluid comprises from5% to about 100% by volume of the oleaginous fluid a material selectedfrom a group consisting of esters, ethers, acetals, di-alkylcarbonates,hydrocarbons, and combinations thereof.
 5. The invert emulsion fluid ofclaim 1 wherein said non-oleaginous fluid comprises from about 1% toabout 70% by volume of said fluid.
 6. The invert emulsion fluid of claim1 wherein said non-oleaginous fluid is an aqueous liquid.
 7. The invertemulsion fluid of claim 6 wherein said aqueous liquid is selected fromthe group consisting of sea water, a brine containing organic orinorganic dissolved sales, a liquid containing water-miscible organiccompounds, and combinations thereof.
 8. The invert emulsion fluid ofclaim 1 wherein R is unsaturated.
 9. The invert emulsion of claim 1wherein the weighting material or bridging agent is selected from thegroup consisting of calcium carbonate, dolomite, siderite, barite,celestite, iron oxides, manganese oxides, ulexite, carnalite, and sodiumchloride.
 10. The invert emulsion of claim 1 wherein said aminesurfactant is selected from diethoxylated tallow amine; diethoxylatedsoya amine; N-aliphatic-1,3-diaminopropane wherein the aliphatic groupis a Cr₁₂ to C₂₂ hydrocarbon; or combinations thereof.
 11. An invertemulsion fluid having utility for drilling completing, or working oversubterranean wells, said fluid comprising: a) an oleaginous liquid, saidoleaginous liquid comprising from about 30% to about 99% by volume ofsaid fluid; b) a non-oleaginous liquid, said non-oleaginous liquidcomprising from about 1% to about 70% by volume of said fluid; c) aweighting agent; d) an amine surfactant present in said fluid at aconcentration of 0.1% to 5.0% by weight of said fluid, said aminesurfactant having a structure of:

 wherein R is a C₁₂-C₂₂ aliphatic hydrocarbon; R′ is an independentlyselectable from hydrogen or C₁ to C₃ alkyl; A is NH or O, and 1<x+y<3;and e) a bridging agent.
 12. The invert emulsion fluid of claim 11wherein said oleaginous liquid is selected from a group consisting ofdiesel oil, mineral oil, a synthetic oil, and combinations thereof. 13.The invert emulsion fluid of claim 12 wherein said oleaginous fluidcomprises from 5% to about 100% by volume of the oleaginous fluid amaterial selected from a group consisting of esters, ethers, acetals,di-alkylcarbonates, hydrocarbons, and combinations thereof.
 14. Theinvert emulsion fluid of claim 13 wherein said non-oleaginous liquid isan aqueous liquid.
 15. The invert emulsion fluid of claim 14 whereinsaid aqueous liquid is selected from the group consisting of sea water,a brine containing organic or inorganic dissolved salts, a liquidcontaining water-miscible organic compounds, and combinations thereof.16. The invert emulsion fluid of claim wherein R is unsaturated.
 17. Theinvert emulsion of claim 11 wherein said amine surfactant is selectedfrom diethoxylated tallow amine; diethoxylated soya amine;N-aliphatic-1,3-diaminopropane wherein the aliphatic group is a C₁₂ toC₂₂ hydrocarbon; or combinations thereof.